S-alkyl carbonimidothioates and their use as aphicides

ABSTRACT

Novel compounds having the formula ##STR1## in which X is hydrogen, mono- or dihalo or 2-methyl; Y is oxygen or sulfur; R is alkyl, lower alkenyl, chloro-lower alkenyl, carbomethoxymethyl or methyl-thiomethyl; and R 1  is lower alkyl, lower alkenyl or p-chlorobenzyl, provided that if X is 4-chloro, R is other than methyl-thiomethyl. The novel compounds of this type possess aphicidal activity 
     Also disclosed is a novel process for making O-(substituted)benzyl thiocarbamate intermediates for these compounds.

DESCRIPTION OF THE INVENTION

This invention relates to novel S-alkyl carbonimidothioates and dithioates. More particularly, this invention relates to novel compounds having the formula ##STR2## in which X is hydrogen, mono- or dihalo or 2-methyl; Y is oxygen or sulfur; R is alkyl, lower alkenyl, chloro-lower alkenyl, carbomethoxymethyl or methyl-thiomethyl; and R₁ is lower alkyl, lower alkenyl or p-chlorobenzyl, provided that if X is 4-chloro, R is other than methyl-thiomethyl.

Preferred embodiments with respect to X are monohalo, especially 2- and 3- halo, and dichloro, more particularly 2-fluoro, 2-chloro, 2-bromo, 2-iodo, 3-chloro, 2,5-dichloro and 3,4-dichloro. In a particularly preferred embodiment, X is 2-chloro, R is alkyl or alkenyl and R₁ is lower alkyl.

By the term "alkyl" is meant to include such groups having either straight chain or branched chain configuration. For example, the alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, nonyl, decyl, dodecyl and the like. In a preferred embodiment, the term "alkyl" includes such groups having from 1 to 15 carbon atoms.

The terms "lower alkyl" and "chloro-lower alkyl" are meant to include such groups having from 1 to 6, preferably from 1 to 4, carbon atoms. For example, the lower alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl and the like and chloro-lower alkyl groups may be various mono- or poly-substituted groups such as chloroethyl, chloropropyl groups and the like.

By the term "lower alkenyl" and "chloro-lower alkenyl" are meant to include such groups having from 2 to 6, preferably from 2 to 4 carbon atoms, in both straight and branched chain configurations. For example, the lower alkenyl group may be vinyl, allyl, 2-methylallyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, crotyl and the like and the chloro-lower alkenyl group may be such a group having from 2 to 4 carbon atoms, for instance, 2-chloroallyl.

In one embodiment Y is oxygen; the compounds are thioates. In another embodiment Y is sulfur; the compounds are dithioates.

In another aspect the invention relates to a method for controlling aphids by applying to the aphid or the habitat thereof an aphicidally effective amount of a compound having the formula ##STR3## in which X, Y, R and R₁ are as defined above. Various methods of controlling aphids involve the use of the various embodiments of the compounds of the present invention mentioned herein.

In general, the compounds of the present invention can be prepared by conversion of an S- or O-benzylthiocarbamate to its sodium salt by treating it with an excess of sodium hydride in tetrahydrofuran. The sodium salt is then reacted with an alkyl halide, preferably an iodide, to yield the final product: ##STR4## The following Examples 1-4 demonstrate the preparation of these compounds.

EXAMPLE 1

N-Methyl, 0-2-chlorobenzyl, S-methallylcarbonimidothioate (Compound 35 herein).

To a 5 l. four-necked flask which contained an argon atmosphere was added 72.0 g. (3.00 moles) of granular sodium hydride and 1500 ml. of dry tetrahydrofuran. A solution of 539 g. (2.50 moles) of 0-2-chlorobenzyl methylthiocarbamate dissolved in 400 cc. of dry tetrahydrofuran was then added dropwise with ice cooling over an interval of 14 minutes and a temperature range of 10°-18° C. The cooling bath was then removed and the mixture was allowed to stir for an additional 11/4 hours at 18°-23° C. Then 340 g. (3.75 moles) of 3-chloro-2-methylpropene which had recently been distilled was added over 6 minutes. The temperature rose from 23° to 35° C during the addition. After the addition an exothermic reaction continued for another hour and the temperature was maintained at about 40° C with appropriate cooling. When the exothermic reaction was over, the temperature was kept at about 40° C for 21/2 more hours by applying heat. The reaction mixture was then cooled to 12° C under a strong argon purge and 300 ml. of ice water was carefully added to decompose the excess sodium hydride.

The mixture was then poured into 2500 ml. of water. The product separated as an oil which was phase separated and was washed with three portions of 500 ml. saturated salt solution. The oil was dried over anhydrous magnesium sulfate, filtered and the cake was washed with 3 small portions of ethyl ether. The combined filtrate was concentrated and evaporated. There was obtained 657 g. (97.4% of theory) of N-methyl, O-2-chlorobenzyl, S-methallylcarbonimidothioate. Gas chromatography showed this product to have a purity of 92.3 area %. The structure was confirmed by NMR (nuclear magnetic resonance) and IR (infra-red) analyses.

EXAMPLE 2

N-Methyl, O-2-chlorobenzyl, S-n-butylcarbonimidothioate (Compound 9 herein).

To a 5 l. four-necked flask which contained an argon atmosphere was added 72.0 g. (3.00 moles) of granular sodium hydride and 1500 ml. of dry tetrahydrofuran. A solution of 539 g. (2.50 moles) of 0-2-chlorobenzyl methylthiocarbamate dissolved in 400 ml. of dry tetrahydrofuran was then added dropwise with ice cooling over an interval of 15 minutes and a temperature range of 8°-17° C. The cooling bath was then removed and the mixture was allowed to stir for an additional hour at 17°-22° C. Then 574 g. (3.12 moles) of 1-iodobutane was added dropwise over 10 minutes. The temperature was kept between 22°-30° C with ice cooling. The cooling bath was then removed and the mixture was stirred an additional 11/4 hour at 25°-27° C. It was then cooled in ice to 8° C under a strong argon purge and 300 ml. of ice water was carefully added to decompose the excess sodium hydride. When no more hydrogen was evolved, the mixture was poured into 2500 ml. of water and the oily product which separated was extracted with 500 ml. of ethyl ether. The ether solution was washed with three portions of 500 ml. saturated salt solution, dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated and evaporated. There was obtained 657 g. (96.7% of theory) of N-methyl, O-2-chlorobenzyl, S-butylcarbonimidothioate. Gas chromatography showed this product to have a purity of 93.5 area %. The structure was confirmed by NMR and IR analyses.

EXAMPLE 3

N-Ethyl, O-2-chlorobenzyl, S-n-propylcarbonimidothioate (Compound 31 herein).

To a 5 l. four-necked flash which contained an argon atmosphere was added 72.0 g. (3.00 moles) of granular sodium hydride and 1900 cc. of dry tetrahydrofuran. Then 574.3 g. (2.50 moles) of O-2-chlorobenzyl ethylthiocarbamate was added dropwise with ice cooling over an interval of 12 minutes at a temperature range of 9°-24° C. The mixture was stirred for 10 minutes and then 510 g. (3.00 moles) of 1-iodopropane was added dropwise over 6 minutes at 26°-40° C with ice cooling. The cooling bath was removed and the mixture was allowed to stir at 34°-27° C for 21/4 hours. It was then cooled in ice to 6° C under strong argon purge and 300 ml. of ice water carefully added to decompose the excess sodium hydride. When no more hydrogen was evolved, the mixture was poured into 2500 ml. of water and the oily product which separated was extracted with 500 ml. of ethyl ether. The ether solution was washed with two 500 ml. portions of saturated salt solution, dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated and evaporated. There was obtained 660 g. (97.1% of theory) of N-ethyl, O-2-chlorobenzyl, S-propylcarbonimidothioate. Gas chromatography showed a purity of 89.4 area %. The structure was confirmed by NMR and IR analyses.

EXAMPLE 4

N-Methyl, S-n-propyl, S-2-chlorobenzylcarbonimidodithioate (Compound 115 herein).

To a 100 cc. three-necked flask under argon was added 0.72 g (0.030 moles) of granular sodium hydride, 25 ml. of dry tetrahydrofuran and 10.20 g. (0.060 moles) of 1-iodopropane. The mixture was cooled to 3° C in an ice bath and then a solution of 4.64 g. (0.020 mole) of S-2-chlorobenzyl methyldithiocarbamate in 5 ml. of dry tetrahydrofuran was added over 6 minutes at 3°-8° C. The mixture was stirred for another hour at 3.5° C and then a few ml. of ethanol was added to decompose the excess sodium hydride. The mixture was poured into 200 ml. of water and the oil which separated was extracted with 150 ml. of ethyl ether. The ether solution was washed with two 50 ml. portions of water, dried over anhydrous magnesium sulfate, filtered, concentrated, and evaporated. There was obtained 5.0 g. (90.9% of theory) of N-methyl, S-propyl, S-2-chlorobenzylcarbonimidothioate. Gas chromatography showed a purity of 90.0 area %. The structure was confirmed by NMR and IR analyses.

The O-benzylthiocarbamates used as the starting materials in Examples 1-3, and analogous compounds for use in preparing the other monothioates disclosed herein, may be prepared by the reaction of an aromatic isothiocyanate with the appropriate benzyl alcohol using potassium tert.-butoxide and methyl sulfoxide, as described by Bauman, J. Chem. & Eng. Data, 11, 274 (1966). However, it has now been found that these O-(substituted) benzylthiocarbamates, which have the formula ##STR5## in which X and R₁ are as previously defined, can be advantageously prepared by a novel process in which the starting benzyl alcohol is first reacted with sodium hydride in tetrahydrofuran and the product reacted with the appropriate isothiocyanate. Example 5 demonstrates this process in the production of O-(2-chlorobenzyl)methylthiocarbamate.

EXAMPLE 5

To a 3 l. four-necked flask under argon was added 26.4 g. (1.10 mole) of granular sodium hydride and 500 ml. of dry tetrahydrofuran. A solution of 142.6 g. (1.00 mole) of 2-chlorobenzyl alcohol dissolved in 250 ml. of dry tetrahydrofuran was then added dropwise over an interval of 42 minutes without any cooling. The temperature rose from 23° to 36° C. The mixture was then heated to reflux (66° C) and held at reflux for 2 hours. It was then cooled to 4° C and a solution of 85.6 g. (1.10 moles) of methyl isothiocyanate, 93.9 area % pure, in 50 ml. of dry tetrahydrofuran, was added over 14 minutes at 4°-14° C with ice cooling. The cooling was removed and the mixture was stirred for an additional 2 hours. A strong argon purge was started and the excess sodium hydride was decomposed by the careful addition of 100 ml. of water. The tetrahydrofuran solvent was removed under reduced pressure and the residual product was drowned in 1500 ml. water. The aqueous mixture was acidified with concentrated hydrochloric acid; solid which formed was extracted with 500 ml. of ethyl ether and the solution was washed with two 250 ml. portions of water, dried over anhydrous magnesium sulfate, filtered, concentrated and evaporated. There was obtained 203.7 g. (94.4% of theory) of O-2-chlorobenzyl methylthiocarbamate, m.p. 62.5°-65.5° C. The structure was confirmed by NMR and IR analyses.

The following Table I lists respective compounds of the present invention which can be prepared according to the above procedures.

                                      Table I                                      __________________________________________________________________________      ##STR6##                                                                                                             m.p. or                                 Compound No.                                                                           X    Y R           R.sub.1     n.sub.D.sup.30                          __________________________________________________________________________     1       2-Cl O CH.sub.3    CH.sub.3    1.5630                                  2       2-Cl O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.5601                                  3       2-Cl O n-C.sub.5 H.sub.11                                                                         CH.sub.3    1.5370                                  4       2-Cl O CH.sub.2CClCH.sub.2                                                                        CH.sub.3    1.5698                                  5       2-F  O C.sub.2 H.sub.5                                                                            CH.sub.3    1.5263                                  6       2-Cl O C.sub.2 H.sub.5                                                                            CH.sub.3    1.5526                                  7       2-Cl O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5456                                  8       2-Cl O i-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5464                                  9       2-Cl O n-C.sub.4 H.sub.9                                                                          CH.sub.3    1.5380                                  10      2-Br O CH.sub.3    CH.sub.3    1.5776                                  11      2-Br O C.sub.2 H.sub.5                                                                            CH.sub.3    1.5679                                  12      2-Br O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5614                                  13      2-Br O i-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5621                                  14      2-Br O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.5749                                  15      2-Br O n-C.sub.4 H.sub.9                                                                          CH.sub.3    1.5542                                  16      2-Br O n-C.sub.5 H.sub.11                                                                         CH.sub.3    1.5487                                  17      2-Br O CH.sub.2CClCH.sub.2                                                                        CH.sub.3    1.5827                                  18      2-F  O CH.sub.3    CH.sub.3    1.5321                                  19      2-Cl O CH.sub.3    C.sub.2 H.sub.5                                                                            54-57.5° C                       20      2-F  O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5219                                  21      2-F  O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.5342                                  22      2-F  O i-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5200                                  23      2-F  O n-C.sub.4 H.sub.9                                                                          CH.sub.3    1.5161                                  24      2-F  O n-C.sub.5 H.sub.11                                                                         CH.sub.3    1.5120                                  25      2-F  O n-C.sub.7 H.sub.15                                                                         CH.sub.3    1.5069                                  26      2-F  O CH.sub.2 CClCH.sub.2                                                                       CH.sub.3    1.5420                                  27      2-Br O n-C.sub.8 H.sub.17                                                                         CH.sub.3    1.5321                                  28      2-I  O CH.sub.3    CH.sub.3    1.5099                                  29      2-I  O C.sub.2 H.sub.5                                                                            CH.sub.3    1.5949                                  30      2-Cl O C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            1.5422                                  31      2-Cl O n-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                            1.5297                                  32      2-Cl O i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                            1.5348                                  33      2-Cl O n-C.sub.4 H.sub.9                                                                          C.sub.2 H.sub.5                                                                            1.5316                                  34      2-Cl O CH.sub.2 CHCH.sub.2                                                                        C.sub.2 H.sub.5                                                                            1.5483                                  35      2-Cl O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.3    1.5520                                  36      2-Cl O CH.sub.2C(CH.sub.3)CH.sub.2                                                                C.sub.2 H.sub.5                                                                            1.6441                                  37      2-Cl O CH.sub.2CClCH.sub.2                                                                        C.sub.2 H.sub.5                                                                            1.5561                                  38      2-F  O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.3    1.5292                                  39      2-Br O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.3    1.5666                                  40      2-I  O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5860                                  41      2-I  O i-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5846                                  42      2-I  O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.5992                                  43      2-I  O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.3    1.5914                                  44      2-I  O n-C.sub.4 H.sub.9                                                                          CH.sub.3    1.5773                                  45      2-I  O n-C.sub.5 H.sub.11                                                                         CH.sub.3    1.5708                                  46      2-Cl O CH.sub.3    n-C.sub.4 H.sub.9                                                                          1.5347                                  47      2-Cl O C.sub.2 H.sub.5                                                                            n-C.sub.4 H.sub.9                                                                          1.5296                                  48      2-Cl O n-C.sub.3 H.sub.7                                                                          n-C.sub.4 H.sub.9                                                                          1.5248                                  49      2-Cl O i-C.sub.3 H.sub.7                                                                          n-C.sub.4 H.sub.9                                                                          1.5234                                  50      2-Cl O CH.sub.2 CHCH.sub.2                                                                        n-C.sub.4 H.sub.9                                                                          1.5357                                  51      2-Cl O n-C.sub.4 H.sub.9                                                                          n-C.sub.4 H.sub.9                                                                          1.5211                                  52      2-Cl O n-C.sub.6 H.sub.13                                                                         CH.sub.3    1.5292                                  53      2-Cl O n-C.sub.7 H.sub.15                                                                         CH.sub.3    1.5252                                  54      2-Cl O n-C.sub.8 H.sub.17                                                                         CH.sub.3    1.5211                                  55      2-Cl O n-C.sub.10 H.sub.21                                                                        CH.sub.3    1.5146                                  56      2-Cl O n-C.sub.12 H.sub.25                                                                        CH.sub.3    1.5105                                  57      2-Cl O C.sub.2 H.sub.5                                                                            n-C.sub.3 H.sub.7                                                                          1.5341                                  58      2-Cl O n-C.sub.3 H.sub.7                                                                          n-C.sub.3 H.sub.7                                                                          1.5310                                  59      3-Cl O CH.sub.3    CH.sub.3    1.5569                                  60      2-Cl O CH.sub.3    n-C.sub.3 H.sub.7                                                                          1.5424                                  61      2-Cl O CH.sub.2 CHCH.sub.2                                                                        n-C.sub.3 H.sub.7                                                                          1.5429                                  62      3-Cl O C.sub.2 H.sub.5                                                                            CH.sub.3    1.5516                                  63      3-Cl O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5449                                  64      3-Cl O i-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5432                                  65      3-Cl O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.5589                                  66      3-Cl O n-C.sub.4 H.sub.9                                                                          CH.sub.3    1.5395                                  67      3-Cl O C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            1.5401                                  68      2,6-Cl                                                                              O C.sub.2 H.sub. 5                                                                           CH.sub.3    1.5654                                  69      2-Cl O CH.sub.2 SCH.sub.3                                                                         CH.sub.2    1.5825                                  70      3-Cl O CH.sub.3    C.sub.2 H.sub.5                                                                            1.5480                                  71      2,6-Cl                                                                              O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5564                                  72      3-Cl O n-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                            1.5340                                  73      3-Cl O CH.sub.2C(CH.sub.3)CH.sub.2                                                                C.sub.2 H.sub.5                                                                            1.5425                                  74      2,6-Cl                                                                              O CH.sub.2C(Ch.sub.3)CH.sub.2                                                                CH.sub.3    1.5643                                  75      2,4-Cl                                                                              O C.sub.2 H.sub.5                                                                            CH.sub.3    1.5633                                  76      2,4-Cl                                                                              O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5549                                  77      2,4-Cl                                                                              O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.3    1.5634                                  78      2-Cl O CH.sub.2 CHCHCH.sub.3                                                                      CH.sub.3    1.5550                                  79      3,4-Cl                                                                              O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5555                                  80      3,4-Cl                                                                              O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.5703                                  81      3,4-Cl                                                                              O CH.sub.2 C(CH.sub.3)CH.sub.2                                                               CH.sub.3    1.5631                                  82      2-Cl O                                                                                 ##STR7##   CH.sub.3    1.5488                                  83      2,5-Cl                                                                              O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5569                                  84      2,5-Cl                                                                              O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    46-49.5° C                       85      2,5-Cl                                                                              O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.3     *                                      86      H    O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5357                                  87      H    O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.5516                                  88      H    O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.3    1.5462                                  89      2-Cl O n-C.sub.3 H.sub.7                                                                          i-C.sub.3 H.sub.7                                                                          1.5288                                  90      2-Cl O CH.sub.2 CHCH.sub.2                                                                        i-C.sub.3 H.sub.7                                                                          1.5404                                  91      2-Cl O CH.sub.2C(CH.sub.3)CH.sub.2                                                                i-C.sub.3 H.sub.7                                                                          1.5364                                  92      2-Cl O n-C.sub.3 H.sub.7                                                                          t-C.sub.4 H.sub.9                                                                          1.5235                                  93      2-Cl O CH.sub.2 CHCH.sub.2                                                                        t-C.sub.4 H.sub.9                                                                          1.5346                                  94      2-Cl O n-C.sub.4 H.sub.9                                                                          t-C.sub.4 H.sub.9                                                                          1.5190                                  95      2-Cl O CH.sub.2 C(CH.sub.3)CH.sub.2                                                               t-C.sub.4 H.sub.9                                                                          1.5323                                  96      2-CH.sub.3                                                                          O n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5362                                  97      2-CH.sub.3                                                                          O CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.5503                                  98      2-CH.sub.3                                                                          O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.3    1.5448                                  99      2-F  O CH.sub.2 CH.sub.2 Cl                                                                       CH.sub.3    1.5406                                  100     2-Cl O n-C.sub.3 H.sub.7                                                                           ##STR8##   1.5783                                  101     2-Cl O CH.sub.2 CH.sub.2 CH.sub.2 Cl                                                              CH.sub.3    1.5601                                  102     2-Cl O n-C.sub.3 H.sub.7                                                                          CH.sub.2 CHCH.sub.2                                                                        1.5461                                  103     2-Cl O CH.sub.2 CHCH.sub.2                                                                        CH.sub.2 CHCH.sub.2                                                                        1.5587                                  104     2-Cl O CH.sub.2C(CH.sub.3)CH.sub.2                                                                CH.sub.2 CHCH.sub.2                                                                        1.5507                                  105     2-Cl O C.sub.2 H.sub.5                                                                             ##STR9##   1.5881                                  106     4-Cl O CH.sub.3    C.sub.2 H.sub.5                                                                            1.5486                                  107     4-Cl O C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            1.5415                                  108     4-Cl O n-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                            1.5366                                  109     4-Cl O n-C.sub.4 H.sub.9                                                                          C.sub.2 H.sub.5                                                                            1.5322                                  110     4-Cl O n-C.sub.5 H.sub.11                                                                         C.sub.2 H.sub.5                                                                            1.5282                                  111     4-Cl O n-C.sub.6 H.sub.13                                                                         C.sub.2 H.sub.5                                                                            1.5254                                  112     4-Cl O n-C.sub.7 H.sub.15                                                                         C.sub.2 H.sub.5                                                                            1.5217                                  113     2-Cl S CH.sub.3    CH.sub.3    1.6062                                  114     2-Cl S C.sub.2 H.sub.5                                                                            CH.sub.3    1.5948                                  115     2-Cl S n-C.sub.3 H.sub.7                                                                          CH.sub.3    1.5879                                  116     2-Cl S CH.sub.2 CHCH.sub.2                                                                        CH.sub.3    1.6005                                  117     2-Cl O CH.sub.2 CHCH.sub.2                                                                         ##STR10##  1.5892                                  118     2-Cl O CH.sub.2C(CH.sub.3)CH.sub.2                                                                 ##STR11##  1.5823                                  119     H    O C.sub.2 H.sub.5                                                                            CH.sub.3    1.5433                                  120     H    O n-C.sub.4 H.sub.9                                                                          CH.sub.3    1.5291                                  121     H    O n-C.sub.5 H.sub.11                                                                         CH.sub.3    1.5261                                  122     H    O C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            1.5280                                  123     H    O n-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                            1.5254                                  124     H    O n-C.sub.4 H.sub.9                                                                          C.sub.2 H.sub.5                                                                            1.5211                                  125     H    O n-C.sub.5 H.sub.11                                                                         C.sub.2 H.sub.5                                                                            1.5172                                  __________________________________________________________________________      *Soapy solid                                                             

Aphicidal Evaluation Tests

Tests were conducted on two species of aphids, namely the black bean aphid, Aphis fabae (Scop.) and the green peach aphid, Myzus persicae (Sulzer) as follows: Black Bean Aphid: Nasturtium plants (Tropaeolum sp.), approximately 5 cm tall, were transplanted into sandy loam soil in 3-inch clay pots and infested with 25-50 black bean aphids of mixed ages. 24 hours later, they were sprayed to the point of runoff with 50-50 acetone-water solutions of the test chemicals. Treated plants were held in the greenhouse and mortality was recorded after 7 days. Test concentrations ranged from 0.05% down to that at which 50% mortality occurred. LD-50 values are expressed below in Table II under the heading "BA" in terms of percent of the test compound in the sprayed solution.

Green Peach Aphid: Radish plants (Rhaphanus sativus), approximately 2 cm tall, were transplanted into sandy loam soil in 3-inch clay pots and infested with 25-50 green peach aphids of mixed ages. 24 hours later they were sprayed to the point of runoff with 50-50 acetone-water solutions of the test chemicals. Treated plants were held in the greenhouse and mortality was recorded after 48 hours. Test concentrations ranged from 0.05% down to that at which 50% mortality occurred. LD-50 values are expressed below in Table II under the heading "GPA" in terms of percent of the test compound in the sprayed solution.

                  Table II                                                         ______________________________________                                                      BA            GPA                                                 Compound No. (%)           (%)                                                 ______________________________________                                         1            0.05          --                                                  2            0.008         0.005                                               3            0.03          --                                                  4            0.01          0.03                                                5            0.003         0.003                                               6            0.0008        0.003                                               7            0.0003        0.003                                               8            0.0008        0.003                                               9            0.0005        0.003                                               10           0.003         0.003                                               11           0.003         0.003                                               12           0.0008        0.003                                               13           0.0008        0.003                                               14           0.0008        0.003                                               15           0.003         0.003                                               16           0.003         0.003                                               17           0.05          --                                                  18           0.005         0.03                                                19           0.005         0.008                                               20           0.0005        0.003                                               21           0.0003        0.003                                               22           0.003         0.003                                               23           0.003         0.003                                               24           0.003         0.005                                               25           0.003         0.003                                               26           0.003         0.003                                               27           0.008         0.05                                                28           0.01          0.03                                                29           0.005         0.003                                               30           0.003         0.005                                               31           0.0003        0.002                                               32           0.0005        0.002                                               33           0.0005        0.003                                               34           0.003         0.003                                               35           0.0005        0.0005                                              36           0.003         0.002                                               37           0.003         0.01                                                38           0.003         0.002                                               39           0.002         0.002                                               40           0.005         0.003                                               41           0.005         0.005                                               42           0.005         0.03                                                43           0.002         0.005                                               44           0.003         0.03                                                45           0.05          --                                                  46           0.003         0.03                                                47           0.01          0.03                                                48           0.002         0.01                                                49           0.03          0.03                                                50           0.0005        0.005                                               51           0.001         0.002                                               52           0.002         0.005                                               53           0.002         0.01                                                54           0.003         0.03                                                55           0.003         0.03                                                56           0.005         >0.05                                               57           0.001         0.005                                               58           0.0005        0.01                                                59           0.005         0.03                                                60           0.005         0.03                                                61           0.002         0.01                                                62           0.005         0.03                                                63           0.003         0.005                                               64           0.005         0.01                                                65           0.003         0.03                                                66           0.005         0.03                                                67           0.05          0.05                                                68           0.05          0.05                                                69           0.002         0.003                                               70           0.01          0.03                                                71           0.04          0.03                                                72           0.01          0.05                                                73           0.005         0.03                                                74           0.05          0.01                                                75           0.03          0.03                                                76           0.03          0.03                                                77           0.05          --                                                  78           0.001         0.005                                               79           0.005         0.05                                                80           0.01          0.05                                                81           0.005         0.03                                                82           0.003         0.03                                                83           0.03          >0.05                                               84           0.05          >0.05                                               85           0.03          >0.05                                               86           0.001         0.005                                               87           0.002         0.01                                                88           0.002         0.003                                               89           0.005         0.03                                                90           0.005         0.03                                                91           0.008         0.03                                                92           0.03          0.03                                                93           0.005         0.03                                                94           0.03          0.03                                                95           0.008         0.03                                                96           0.002         0.002                                               97           0.002         0.003                                               98           0.003         0.002                                               99           0.05          0.03                                                100          0.05          --                                                  101          0.002         0.003                                               102          0.0005        0.005                                               103          0.002         0.01                                                104          0.002         0.005                                               105          0.002         0.005                                               106          0.03          0.03                                                107          0.03          0.03                                                108          0.01          0.03                                                109          0.03          0.01                                                110          0.03          0.03                                                111          0.05          0.03                                                112          >0.05         0.03                                                113          0.03          0.03                                                114          0.05          --                                                  115          0.005         0.03                                                116          0.01          0.03                                                117          0.03          >0.05                                               118          0.03          >0.05                                               119          0.003         0.005                                               120          0.002         0.002                                               121          0.01          0.005                                               122          0.008         0.005                                               123          0.001         0.01                                                124          0.003         0.008                                               125          0.005         0.005                                               ______________________________________                                    

The compounds of this invention are generally embodied into a form suitable for convenient application. For example, the compounds can be embodied into aphicidal compositions which are provided in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such compositions will contain, in addition to the active compounds, the adjuvants which are found normally in aphicidal preparations. In these compositions, the active compounds of this invention can be employed as the sole pesticidal component or they can be used in admixture with other compounds having similar utility. The pesticidal compositions of this invention can contain, as adjuvants, appropriate inert carriers or diluents, for example, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum, etc.; water; emulsifying agents; surface active agents; talc; pyrophyllite, diatomite; gypsum; clays, propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc., upon which the pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In connection with the activity of the presently disclosed aphicidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.

The precise manner in which the aphicidal compositions containing compounds of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active compound will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol spray. While the concentration of the active aphicide in the present compositions can vary within rather wide limits, ordinarily the aphicidal compound will comprise between about 0.01 and about 80% by weight of the composition. 

What is claimed is:
 1. A compound having the formula ##STR12## in which X is hydrogen, mono- or dihalo or 2-methyl; Y is oxygen or sulfur; R is alkyl, lower alkenyl, chloro-lower alkyl, chloro-lower alkenyl, carbomethoxymethyl or methyl-thiomethyl and R₁ is lower alkyl, lower alkenyl or p-chlorobenzyl; provided that if X is 4-chloro, R is other than methyl-thiomethyl.
 2. A compound according to claim 1 in which X is mono-halo.
 3. A compound according to claim 2 in which X is mono-chloro.
 4. A compound according to claim 3 in which X is 2-chloro.
 5. A compound according to claim 3 in which X is 3-chloro.
 6. A compound according to claim 2 in which X is 2-fluoro.
 7. A compound according to claim 2 in which X is 2-bromo.
 8. A compound according to claim 2 in which X is 2-iodo.
 9. A compound according to claim 1 in which X is dichloro.
 10. A compound according to claim 9 in which X is 2,5-dichloro.
 11. A compound according to claim 9 in which X is 3,4-dichloro.
 12. A compound according to claim 1 in which X is 2-methyl.
 13. A compound according to claim 1 in which X is hydrogen.
 14. A compound according to claim 1 in which Y is oxygen.
 15. A compound according to claim 1 in which Y is sulfur.
 16. A compound according to claim 1 in which R is alkyl.
 17. A compound according to claim 16 in which R is methyl.
 18. A compound according to claim 16 in which R is ethyl.
 19. A compound according to claim 16 in which R is n-propyl.
 20. A compound according to claim 16 in which R is isopropyl.
 21. A compound according to claim 16 in which R is n-butyl.
 22. A compound according to claim 1 in which R is lower alkenyl.
 23. A compound according to claim 22 in which R is allyl.
 24. A compound according to claim 22 in which R is 2-methylallyl.
 25. A compound according to claim 1 in which R is 2-chloroallyl.
 26. A compound according to claim 1 in which R is 3-chloropropyl.
 27. A compound according to claim 1 in which R₁ is lower alkyl.
 28. A compound according to claim 27 in which R₁ is methyl.
 29. A compound according to claim 27 in which R₁ is ethyl.
 30. A compound according to claim 27 in which R₁ is n-propyl.
 31. A compound according to claim 27 in which R₁ is n-butyl.
 32. A compound according to claim 1 in which R₁ is lower alkenyl.
 33. A compound according to claim 32 in which R₁ is allyl.
 34. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is methyl and R₁ is methyl.
 35. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is allyl, and R₁ is methyl.
 36. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-pentyl, and R₁ is methyl.
 37. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is 2-chloroallyl and R₁ is methyl.
 38. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is ethyl and R₁ is methyl.
 39. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is ethyl and R₁ is methyl.
 40. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is methyl.
 41. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is isopropyl and R₁ is methyl.
 42. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-butyl and R₁ is methyl.
 43. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is ethyl and R₁ is methyl.
 44. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is methyl and R₁ is methyl.
 45. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is n-propyl and R₁ is methyl.
 46. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is isopropyl and R₁ is methyl.
 47. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is allyl and R₁ is methyl.
 48. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is n-butyl and R₁ is methyl.
 49. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is n-pentyl and R₁ is methyl.
 50. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is 2-chloroallyl and R₁ is methyl.
 51. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is methyl and R₁ is methyl.
 52. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is methyl and R₁ is ethyl.
 53. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is n-propyl, and R₁ is methyl.
 54. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is allyl and R₁ is methyl.
 55. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is isopropyl and R₁ is methyl.
 56. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is n-butyl and R₁ is methyl.
 57. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is n-pentyl and R₁ is methyl.
 58. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is n-heptyl and R₁ is methyl.
 59. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is 2-chloroallyl and R₁ is methyl.
 60. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is n-octyl, and R₁ is methyl.
 61. A compound according to claim 1 in which X is 2-iodo, Y is oxygen, R is methyl and R₁ is methyl.
 62. A compound according to claim 1 in which X is 2-iodo, Y is oxygen, R is ethyl and R₁ is methyl.
 63. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is ethyl and R₁ is ethyl.
 64. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is ethyl.
 65. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is isopropyl and R₁ is ethyl.
 66. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-butyl and R₁ is ethyl.
 67. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is allyl and R₁ is ethyl.
 68. A compound according to claim 1 in which X 2-chloro, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 69. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is 2-methylallyl and R₁ is ethyl.
 70. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is 2-chloroallyl and R₁ is ethyl.
 71. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 72. A compound according to claim 1 in which X is 2-bromo, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 73. A compound according to claim 1 in which X is 2-iodo, Y is oxygen, R is n-propyl and R₁ is methyl.
 74. A compound according to claim 1 in which X is 2-iodo, Y is oxygen, R is isopropyl and R₁ is methyl.
 75. A compound according to claim 1 in which X is 2-iodo, Y is oxygen, R is allyl and R₁ is methyl.
 76. A compound according to claim 1 in which X is 2-iodo, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 77. A compound according to claim 1 in which X is 2-iodo, Y is oxygen, R is n-butyl and R₁ is methyl.
 78. A compound according to claim 1 in which X is 2-iodo, Y is oxygen, R is n-pentyl and R₁ is methyl.
 79. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is methyl and R₁ is n-butyl.
 80. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is ethyl and R₁ is n-butyl.
 81. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is n-butyl.
 82. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is isopropyl and R₁ is n-butyl.
 83. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is allyl and R₁ is n-butyl.
 84. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-butyl and R₁ is n-butyl.
 85. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-hexyl and R₁ is methyl.
 86. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-heptyl and R₁ is methyl.
 87. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-octyl and R₁ is methyl.
 88. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-decyl and R₁ is methyl.
 89. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-dodecyl and R₁ is methyl.
 90. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is ethyl and R₁ is n-propyl.
 91. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is n-propyl.
 92. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is methyl and R₁ is methyl.
 93. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is methyl and R₁ is n-propyl.
 94. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is allyl and R₁ is n-propyl.
 95. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is ethyl and R₁ is methyl.
 96. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is n-propyl and R₁ is methyl.
 97. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is isopropyl and R₁ is methyl.
 98. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is allyl and R₁ is methyl.
 99. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is n-butyl and R₁ is methyl.
 100. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is ethyl and R₁ is ethyl.
 101. A compound according to claim 1 in which X is 2,6-dichloro, Y is oxygen, R is ethyl and R₁ is methyl.
 102. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is methyl-thiomethyl and R₁ is methyl.
 103. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is methyl and R₁ is ethyl.
 104. A compound according to claim 1 in which X is 2,6-dichloro, Y is oxygen, R is n-propyl and R₁ is methyl.
 105. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is n-propyl and R₁ is ethyl.
 106. A compound according to claim 1 in which X is 3-chloro, Y is oxygen, R is 2-methylallyl and R₁ is ethyl.
 107. A compound according to claim 1 in which X is 2,6-dichloro, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 108. A compound according to claim 1 in which X is 2,4-dichloro, Y is oxygen, R is ethyl and R₁ is methyl.
 109. A compound according to claim 1 in which X is 2,4-dichloro, Y is oxygen, R is n-propyl and R₁ is methyl.
 110. A compound according to claim 1 in which X is 2,4-dichloro, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 111. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is crotyl and R₁ is methyl.
 112. A compound according to claim 1 in which X is 3,4-dichloro, Y is oxygen, R is n-propyl and R₁ is methyl.
 113. A compound according to claim 1 in which X is 3,4-dichloro, Y is oxygen, R is allyl and R₁ is methyl.
 114. A compound according to claim 1 in which X is 3,4-dichloro, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 115. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is carbomethoxymethyl and R₁ is methyl.
 116. A compound according to claim 1 in which X is 2,5-dichloro, Y is oxygen, R is n-propyl and R₁ is methyl.
 117. A compound according to claim 1 in which X is 2,5-dichloro, Y is oxygen, R is allyl and R₁ is methyl.
 118. A compound according to claim 1 in which X is 2,5-dichloro, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 119. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is n-propyl and R₁ is methyl.
 120. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is allyl and R₁ is methyl.
 121. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 122. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is isopropyl.
 123. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is allyl and R₁ is isopropyl.
 124. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is 2-methylallyl and R₁ is isopropyl.
 125. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is tert.-butyl.
 126. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is allyl and R₁ is tert.-butyl.
 127. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-butyl and R₁ is tert.-butyl.
 128. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is 2-methylallyl and R₁ is tert.-butyl.
 129. A compound according to claim 1 in which X is 2-methyl, Y is oxygen, R is n-propyl and R₁ is methyl.
 130. A compound according to claim 1 in which X is 2-methyl, Y is oxygen, R is allyl and R₁ is methyl.
 131. A compound according to claim 1 in which X is 2-methyl, Y is oxygen, R is 2-methylallyl, and R₁ is methyl.
 132. A compound according to claim 1 in which X is 2-fluoro, Y is oxygen, R is 2-chloroethyl and R₁ is methyl.
 133. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is p-chlorobenzyl.
 134. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is 3-chloropropyl and R₁ is methyl.
 135. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is allyl.
 136. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is allyl, and R₁ is allyl.
 137. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is 2-methylallyl and R₁ is allyl.
 138. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is ethyl and R₁ is p-chlorobenzyl.
 139. A compound according to claim 1 in which X is 4-chloro, Y is oxygen, R is methyl and R₁ is ethyl.
 140. A compound according to claim 1 in which X is 4-chloro, Y is oxygen, R is ethyl and R₁ is ethyl.
 141. A compound according to claim 1 in which X is 4-chloro, Y is oxygen, R is n-propyl and R₁ is ethyl.
 142. A compound according to claim 1 in which X is 4-chloro, Y is oxygen, R is n-butyl and R₁ is ethyl.
 143. A compound according to claim 1 in which X is 4-chloro, Y is oxygen, R is n-pentyl and R₁ is ethyl.
 144. A compound according to claim 1 in which X is 4-chloro, Y is oxygen, R is n-hexyl and R₁ is ethyl.
 145. A compound according to claim 1 in which X is 4-chloro, Y is oxygen, R is n-heptyl and R₁ is ethyl.
 146. A compound according to claim 1 in which X is 2-chloro, Y is sulfur, R is methyl and R₁ is methyl.
 147. A compound according to claim 1 in which X is 2-chloro, Y is sulfur, R is ethyl and R₁ is ethyl.
 148. A compound according to claim 1 in which X is 2-chloro, Y is sulfur, R is n-propyl, and R₁ is methyl.
 149. A compound according to claim 1 in which X is 2-chloro, Y is sulfur, R is allyl and R₁ is methyl.
 150. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is allyl and R₁ is p-chlorobenzyl.
 151. A compound according to claim 1 in which X is 2-chloro, Y is oxygen, R is 2-methylallyl and R₁ is p-chlorobenzyl.
 152. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is ethyl and R₁ is methyl.
 153. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is n-butyl and R₁ is methyl.
 154. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is n-pentyl and R₁ is methyl.
 155. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is ethyl and R₁ is ethyl.
 156. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is n-propyl and R₁ is ethyl.
 157. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is n-butyl and R₁ is ethyl.
 158. A compound according to claim 1 in which X is hydrogen, Y is oxygen, R is n-pentyl and R₁ is ethyl.
 159. A method for controlling aphids comprising applying to the aphid or the habitat thereof an aphicidally effective amount of a compound having the formula ##STR13## in which X is hydrogen, mono- or dihalo or 2-methyl; Y is oxygen or sulfur, R is alkyl, lower alkenyl, halo-lower alkyl, halo-lower alkenyl, carbomethoxymethyl or methylthiomethyl and R₁ is lower alkyl, lower alkenyl or p-chlorobenzyl, provided that if X is 4-chloro, R is other than methylthiomethyl.
 160. A method according to claim 159 in which X is halo.
 161. A method according to claim 159 in which X is chloro.
 162. A method according to claim 161 in which X is 2-chloro.
 163. A method according to claim 161 in which X is 3-chloro.
 164. A method according to claim 160 in which X is 2-fluoro.
 165. A method according to claim 160 in which X is 2-bromo.
 166. A method according to claim 160 in which X is 2-iodo.
 167. A method according to claim 159 in which X is dichloro.
 168. A method according to claim 167 in which X is 2,5-dichloro.
 169. A method according to claim 167 in which X is 3,4-dichloro.
 170. A method according to claim 159 in which X is 2-methyl.
 171. A method according to claim 159 in which X is hydrogen.
 172. A method according to claim 159 in which Y is oxygen.
 173. A method according to claim 159 in which Y is sulfur.
 174. A method according to claim 159 in which R is alkyl.
 175. A method according to claim 174 in which R is methyl.
 176. A method according to claim 174 in which R is ethyl.
 177. A method according to claim 174 in which R is n-propyl.
 178. A method according to claim 174 in which R is isopropyl.
 179. A method according to claim 174 in which R is n-butyl.
 180. A method according to claim 159 in which R is lower alkenyl.
 181. A method according to claim 180 in which R is allyl.
 182. A method according to claim 180 in which R is 2-methylallyl.
 183. A method according to claim 159 in which R is 2-chloroallyl.
 184. A method according to claim 159 in which R is 3-chloropropyl.
 185. A method according to claim 159 in which R₁ is lower alkyl.
 186. A method according to claim 185 in which R₁ is methyl.
 187. A method according to claim 185 in which R₁ is ethyl.
 188. A method according to claim 185 in which R₁ is n-propyl.
 189. A method according to claim 185 in which R₁ is n-butyl.
 190. A method according to claim 159 in which R₁ is lower alkenyl.
 191. A method according to claim 190 in which R₁ is allyl.
 192. A method according to claim 159 in which X is 2-chloro, Y is oxygen, R is n-butyl and R₁ is methyl.
 193. A method according to claim 159 in which X is 2-chloro, Y is oxygen, R is n-propyl and R₁ is ethyl.
 194. A method according to claim 159 in which X is 2-chloro, Y is oxygen, R is 2-methylallyl and R₁ is methyl.
 195. An aphicidal composition of matter comprising:a. an aphicidally effective amount of a compound having the formula ##STR14## in which X is hydrogen, mono- or dihalo, or 2-methyl; Y is oxygen or sulfur, R is alkyl, lower alkenyl, chloro-lower alkyl, chloro-lower alkenyl, carbomethoxymethyl or methylthiomethyl; and R₁ is lower alkyl, lower alkenyl or p-chlorobenzyl, provided that if X is 4-chloro, R is other than methylthiomethyl. 